Construction Of Aromatic Or Heteroaromatic Ring On Dehydroabietic Acid Skeleton And Study On The Products' Fluorenscence Property

Dehydroabietic acid(DAA) is one of the isomerides in the renewable rosin. It is widely used in the fields such as paint, adhesives, printing ink, papermaking, rubber food, etc. Like some natural drug, it has a aromatic diterpene structure with three ring. It also has three chiral carbon atom and a reactive carboxy group. For these reasons, DAA might be hopefully modified to some multifunctional derivatives which can use as high added value products like novel fluorescence derivatization reagents and efficient but low toxic medicines through constructing aromatic or heteroaromatic ring on DAA's skeleton. It not only meet with the de)and of green chemistry but also bring about favorable economical and social effects. In this paper, we firstly studied the rearrang_ement of DAA derivatives. Its'methyl ester and 12 bromo methyl ester were respectively oxidized, reduced and then rearranged under the existence of lewis acid to tetrahydroanthracene derivatives with fluorescent λex/λ_em of 280-290nm/345-355nm. Compared with DAA's methyl ester, both the products'maximal excitation wavelengths andemission wavelengths are red shifted. Methyl 12-bromo-13-nitro-deisopropyldehydroabietate was lastly rearranged to different products under the same conditions however. One of the products was naphthalene compound and the other was tetrahydrophenanthrene compound. Using 2D-NMR, we studied their fine structures. Among them, the naphthalene compound has a skeleton firstly observed in DAA's rearrangement products. A possible mechanism of the rearrangement reactions is discussed. Then, 12-aminodehydroabietate and cis-12-aminodeisopropyldehydroabietate were coupled respectively with 2-chloro-3,5-dinitrobenzoic acid. Their products were cyclized with POCl3 and further hydrolyzed to red acridones. Three other intermediate compounds which can be used to the synthesis of other acridones were also synthesized. The three acridonesemit fluorescence of 310-330 nm ifexcited by a violet light ranging 280-290 nm. These bright-coloured products have good properties forexploiting novel dyes. By coupled with glycerol, cis-12-aminodeisopropyldehydroabietate were converted to quinolines with fluorescent λ_ex/ λ_em of 255-260nm/370-380nm. 12-bromo-13,14-dinitro-deisopropyldehydroabietate was reduced , diazotized to triazoles with fluorescent λ_ex/λ_em of 293nm/364nm. In addition, two N-DAAmaleimides were synthesized by the reaction of 12-aminodehydroabietate, 12-amino-14-nitrodehydroabietate with maleic anhydride respectively. The TGA curves showed that two products lost half weight at 466℃and 442℃respectively. It indicates products'good thermostability. The nitromaleimide is nonfluorescent substance and the another maleimideemit fluorescence of 402 nm ifexcited by a violet light ranging 268 nm. In summary, 16 new compounds were synthesized and characterized by IR, NMR and MS in this paper. Our study shows that DAA's properties such as fluorescence, thermostability were improved through constructing aromatic or heteroaromatic ring on DAA's skeleton. All that laid the groundwork for futureexploitation of multifunctional reagents.